JPH07505430A - Stabilizer composition for halogen-containing polymers and the above-mentioned containing polymer composition - Google Patents
Stabilizer composition for halogen-containing polymers and the above-mentioned containing polymer compositionInfo
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- JPH07505430A JPH07505430A JP5517435A JP51743593A JPH07505430A JP H07505430 A JPH07505430 A JP H07505430A JP 5517435 A JP5517435 A JP 5517435A JP 51743593 A JP51743593 A JP 51743593A JP H07505430 A JPH07505430 A JP H07505430A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 ハロゲン含有ポリマー類用安定剤組成物および上記含有ポリマー組代物 本発明は、ハロゲン含有ポリマー類、特に塩化ビニルポリマー類のための安定剤 組成物、並びに上記組成物を含有しているポリマー調合物１こ関するものである 。[Detailed description of the invention] Stabilizer composition for halogen-containing polymers and the above-mentioned containing polymer compound The present invention provides stabilizers for halogen-containing polymers, especially vinyl chloride polymers. 1 composition and a polymer formulation containing said composition. .
２ 発明の発明 ハロゲン含有ポリマー類、より一般的には塩化ビニルポリマー類（ＰＶＣ）は、 特にオフィスビルディングなどで用いるためのワイヤー絶縁およびケーブル用ジ ャケットを製造する目的で通常に用（１られて（する。2 Invention of invention Halogen-containing polymers, more commonly vinyl chloride polymers (PVC), are Wire insulation and cable insulation especially for use in office buildings etc. It is commonly used for the purpose of manufacturing jackets.
ＰＶＣ絶縁体および／またはケーブル用ジャケットに熱安定性を与える目的で種 々の熱安定剤が組み込まれている。特に、このようなＰＶＣ調合物における熱安 定剤としては、鉛の塩類が用いられてＩ、Ｎる。鉛を基とする安定剤は、熱安定 性を与えると共に、一般にそのポリマー調合物に良好な電気的絶縁特性を与える 。Seeds are added to provide thermal stability to PVC insulation and/or cable jackets. Various heat stabilizers are incorporated. In particular, thermal stability in such PVC formulations As a fixing agent, lead salts are used. Lead-based stabilizers are heat stable properties and generally provide good electrical insulation properties to the polymer formulation. .
健康および環境上の関心が高まって来たことから、ＰＶＣおよび他のハロゲン含 有ポリマー組成物の中に人っているこれらの鉛を基とする熱安定剤を置き換えよ うとする試みが成されてきた。例えば、通常のＰＶＣ用熱用足安定剤ンチモンと 錫塩の混合物を含んでいる。このような安定剤は、健康および環境上の観点から すると、鉛を基とする安定剤よりも好ましいが、これらは一般に、鉛を基とする 熱安定剤を用Ｗこ時達成され得る程の電気的絶縁特性を与えない。Due to increasing health and environmental concerns, PVC and other halogen-containing Replace these lead-based heat stabilizers in polymeric compositions. Attempts have been made to For example, with the normal PVC thermal foot stabilizer Nthimon, Contains a mixture of tin salts. Such stabilizers are important from a health and environmental point of view. These are generally preferable to lead-based stabilizers, which are The use of thermal stabilizers does not provide as much electrical insulation properties as can be achieved at this time.
理想的には、ハロゲン含有ポリマー組成物のための熱安定剤には重金属塩、例え ば鉛塩などが含まれているべきでないが、これは、鉛の塩類を用いた時に達成さ れる熱安定性および電気絶縁特性に相当しているか或はそれよりも優れている熱 安定性と電気絶縁特性を与えるべきである。Ideally, heat stabilizers for halogen-containing polymer compositions include heavy metal salts, e.g. This should not be achieved when using lead salts. thermal stability and electrical insulation properties equivalent to or superior to It should provide stability and electrical insulation properties.
発明の要約 従って、本発明の１つの目的は、ハロゲン含有ポリマー内で用いるための改良さ れた安定剤組成物を提供することにある。Summary of the invention Accordingly, one object of the present invention is to provide an improved method for use in halogen-containing polymers. An object of the present invention is to provide a stabilizer composition that is improved in quality.
本発明の別の目的は、重金属の塩類を用いていないハロゲン含有ポリマー類用安 定剤組成物を提供することにある。Another object of the present invention is to provide a safe solution for halogen-containing polymers without heavy metal salts. An object of the present invention is to provide a fixing agent composition.
本発明の更に別の目的は、重金属塩類が入っていない熱安定剤を含んでいるハロ ゲン含有ポリマー組成物を提供することにある。Yet another object of the invention is to provide a halogen containing heat stabilizer free of heavy metal salts. An object of the present invention is to provide a polymer composition containing gen.
本発明の上記および他の目的は、本明細書および請求の範囲に示す記述から明ら かになるであろう。The above and other objects of the present invention will be apparent from the description set forth in the specification and claims. It will be something like that.
１つの面において、本発明は、一般式 ％式％ ［式中、 ＸはＯから０５の数であり、ＡはＣ０１−または５Ｏ４−であり、そしてＭは、 この分子内のＨ２Ｃ数を表している数である］て表される水滑石と一般式・ Ｍ ２７゜Ｏ，Ａｈ０３．ｙＳｉＯ２ｗＨ２０［式中、 Ｍは、ＩＡ族および−■Ａ族元素から選択される金属のカチオンであり、ｙは２ またはそれ以上であり、ｎは該カチオンの原子価であり、そしてＷは、このゼオ ライトの空隙内に含まれている水を表している］で表されるモレキュラーシーブ ゼオライトを含んでおり、ここで、このゼオライト内のＳｉ／ＡＩ比が約１以上 であり、そしてここで、この水滑石とゼオライトの重量比が約０．５：１から約 ３：１である、ハロゲン合有ポリマー類内で用いるための安定剤組成物を提供す る。In one aspect, the invention provides the general formula %formula% [In the formula, X is a number from 0 to 05, A is C01- or 5O4-, and M is This is the number representing the number of H2C in this molecule] and the general formula: M 27゜O, Ah03. ySiO2wH20 [wherein, M is a metal cation selected from group IA and -■A group elements, and y is 2 or more, n is the valence of the cation, and W is the valence of the zeolite. Molecular sieve represented by [representing water contained within the light voids] contains zeolite, where the Si/AI ratio within the zeolite is about 1 or more. and where the weight ratio of hydrotalcite to zeolite is from about 0.5:1 to about 3:1 stabilizer composition for use in halogen-containing polymers. Ru.
本発明の別の面において、上に記述した安定剤組成物の有効量とハロゲン含有ポ リマーを含んでいる組成物を提供する。In another aspect of the invention, an effective amount of the stabilizer composition described above and a halogen-containing polymer are provided. A composition comprising a remer is provided.
好適な態様の説明 本発明の安定剤組成物は、２種の主要材料である（１）水滑石と（２）モレキュ ラーシーブゼオライトを含んでいる。本発明の安定剤組成物内で用いる水滑石は 、一般式。Description of preferred embodiments The stabilizer composition of the present invention consists of two main materials: (1) Hydrotalcite and (2) Molecule. Contains Rashib zeolite. The hydrotalcite used within the stabilizer composition of the present invention is , general expression.
Ｍｇ＋−、Ａ１．（ＯＨ）ｚＡ、ｚｚＨｍＨｚ。Mg+-, A1. (OH)zA, zzHmHz.
［式中、 ８はＯから０． ５の数であり、ＡはＣＯ３−または５０４−であり、そしてｍ は、この分子内のＨ，Ｏ数を表している数である］で表される。用いられ得る水 滑石には、天然に存在している種々の鉱物水滑石、並びに上記式内に入る合成水 滑石が含まれる。上記水滑石は、それらの高級脂肪酸アルカリ金属塩の形態が或 は有機スルホン酸アルカリ金属塩の形態で用いられ得る。特に好適なものは、Ｘ が約０．１から約０． ４の数であり、ＡがＣＯ３−でありモしてｍが約０． ４から約０゜７である水滑石、例えばＸが０．３３であり、Ａが００３−であり そしてｍが０５である水滑石である。[In the formula, 8 is from O to 0. 5, A is CO3- or 504-, and m is a number representing the number of H and O in this molecule]. water that can be used Talc includes various naturally occurring minerals hydrotalc, as well as synthetic water that falls within the above formula. Contains talc. The above-mentioned hydrotalcites have different forms of higher fatty acid alkali metal salts. may be used in the form of an alkali metal organic sulfonic acid salt. Particularly suitable are X is about 0.1 to about 0. 4, A is CO3-, and m is about 0. 4 to about 0°7, e.g. where X is 0.33 and A is 003- And it is hydrotalcite with m being 05.
この安定剤組成物のもつ１つの主要成分は、一般式％式％ ［式中、 Ｍは、ＩＡ族およびＩＩＡ族元素から選択される金属のカチオンであり、ｙは２ またはそれ以上であり、ｎは該カチオンの原子価であり、モしてＷは、このゼオ ライトの空隙内に含まれている水を表しており、ここで、このゼオライト内のＳ ｉ／ＡＩ比は約１以上である］で表されるモレキュラーシーブゼオライトである 。このゼオライトは、約５オングストローム以上、好適には約１０オングストロ ーム以上の平均孔サイズを有する種類のものであるのが好適である。また、Ａゼ オライトではな（Ｘゼオライトを用いる方が好適である。また好適なものは、必 ずしもではないが、カチオンＭがアルカリ金属、特にナトリウムであるものであ る。本発明の組成物で有効なゼオライト類に関する考察に関しては、ｒＥＮｃＹ ｃＬＯＰＥＤＩＡ ＯＦ ＣＨＥＭＩＣＡＬ ＴＥＣＨＮＯＬＯＧＹＪ、１９８ １、第１５巻、６３８−６５３頁（全ての目的で引用することによって本明細書 に組み入れられる）を参照のこと。One major component of this stabilizer composition has the general formula %. [In the formula, M is a metal cation selected from Group IA and Group IIA elements, and y is 2 or more, n is the valence of the cation, and W is the valence of the cation. It represents the water contained within the pores of the zeolite, and here, the S is a molecular sieve zeolite with an i/AI ratio of about 1 or more. . The zeolite is about 5 angstroms or more, preferably about 10 angstroms or more. Preferably, the pore size is of a type having an average pore size greater than or equal to the average pore size of the pore size. Also, Aze It is preferable to use zeolite (X zeolite). It is not necessarily true that the cation M is an alkali metal, especially sodium. Ru. For a discussion of zeolites useful in compositions of the invention, see rENcY cLOPEDIA OF CHEMICAL TECHNOLOGYJ, 198 1, Volume 15, pp. 638-653 (herein incorporated by reference for all purposes) (incorporated into).
この安定剤組成物では、この水滑石とゼオライトの重量比が約０． ５＝１から 約３：１になるようにこの水滑石とゼオライトを用いる。In this stabilizer composition, the weight ratio of hydrotalcite to zeolite is about 0. From 5=1 This water talc and zeolite are used in a ratio of about 3:1.
この水滑石とゼオライトに加えて、本発明の安定剤組成物はまた、有利にベータ ージケトンを含んでいてもよい。米国特許第４． ４２７． ８１６号に開示さ れているように、ハロゲン含有ポリマー類の熱劣化および光劣化に対する抵抗力 を増強する目的で、これらのポリマー類の安定剤組成物として、ベータージケト ン類と水滑石を有利に用いることができる。本発明の組成物内で有効性を示すベ ータージケトン類は開示されており、米国特許第４，４２７．８１６号（全ての 目的で引用することによって本明細書に組み入れられる）の中で請求されている 。特に、有効なベータージケトン類は、この米国特許第４゜４２７，８１６号の コラム２の１１行からコラム３の６行の中に記述されている。このベータージケ トンを用いる場合、これは、その安定剤組成物内に有効量で存在しており、その 量は一般に、この安定剤組成物の約１から約１５重量％を構成している。In addition to this hydrotalcite and zeolite, the stabilizer composition of the present invention also advantageously contains beta -diketones may be included. U.S. Patent No. 4. 427. Disclosed in No. 816 The resistance of halogen-containing polymers to thermal and photodegradation, as shown in Beta-diketo is used as a stabilizer composition for these polymers in order to enhance minerals and hydrotalc can be used advantageously. Bases showing efficacy within the compositions of the invention -terdiketones have been disclosed in U.S. Pat. No. 4,427.816 (all (incorporated herein by reference) . Particularly effective beta-diketones are described in U.S. Pat. No. 4,427,816. It is described from column 2, line 11 to column 3, line 6. This beta If a ton is used, it is present in the stabilizer composition in an effective amount and its Amounts generally constitute from about 1 to about 15% by weight of the stabilizer composition.
本発明の安定剤組成物は、４０重量％以上のハロゲン含有量を有している、少な くとも部分的に下記の繰り返しくｒｅ−ｏｃｃｕｒｒ ｉｎｇ）基・ Ｚｌはハロゲンてあり、モしてＺフはハロゲンまたは水素のどちらかである］ て出来ているポリハロゲン化ビニル樹脂が含まれているポリハロゲン化ビニル瘤 脂組成物内で有利に用いられる。これらは、ＰＶｃ組成物、例えば塩化ビニルの ホモポリマー類か或は塩化ビニルと少なくとも１種の池の共重合性モノマーとの 共重合体などの中で特に有効性を示す。本発明の安定剤組成物を上記ハロゲン含 有ポリマー頬内で用いる時、これらは−役に有効量、即ち充分な熱安定性と満足 される電気絶縁特性を与えるに充分な量で存在している。より一般的には、この 安定剤組成物は、上記ハロゲン含有ポリマー樹脂内に（耐脂１００部当たり約０ ５がら約１０部（ｐｈｒ）のｊｌｌズ存在しテイル。The stabilizer composition of the present invention has a halogen content of 40% by weight or more. At least partially the following repeating re-occurring) group: Zl is halogen, and Zf is either halogen or hydrogen] Polyhalogenated vinyl aneurysms containing polyhalogenated vinyl resin made from Advantageously used within fat compositions. These include PVc compositions, e.g. Homopolymers or vinyl chloride with at least one copolymerizable monomer It is particularly effective among copolymers. The above halogen-containing stabilizer composition of the present invention When used intrabuccally, these polymers can be used in - usefully effective amounts, i.e. with sufficient thermal stability and present in an amount sufficient to provide electrical insulating properties. More generally, this A stabilizer composition is incorporated into the halogen-containing polymer resin (about 0 parts per 100 parts of greaseproofing). There are about 10 copies (phr) of Jlls from 5 to 10000000000000000000000000000000000000000000000000000000000000000000000 type type type form type form form type form type form form type form, 10 types (phr) form to form.
以下に与えるデータが示すように、この水滑石とゼオライトを用いると、一般に 、電気絶縁特性、特に体積抵抗（ＶＲ）の如き特性の観点で相乗結果が得られる 。As the data given below shows, with this hydrotalcite and zeolite, generally , synergistic results can be obtained in terms of electrical insulation properties, especially properties such as volume resistance (VR). .
本発明を更に詳しく説明する目的で、下記の非制限的実施例を示す。In order to further illustrate the invention, the following non-limiting examples are presented.
全ての場合において、樹脂１００部当ｌ９の部数（ｐｈｒ）でこれらの組成を示 す。In all cases, these compositions are expressed in parts per 100 parts of resin (phr). vinegar.
実施例１ １組のｐｖｃｍ脂調合物を用いてグラベンダー安定性試験を実施した。Example 1 Gravender stability testing was performed using a set of pvcm fat formulations.
基本となる樹脂調合物は下記の通りであった二材料 ＰＨＲ ｐｖｃ４Ｈ脂ｉ ｏ ｏ、 。The basic resin formulation was as follows: PHR pvc4H fat i o o.
トリメリット酸トリオクチル ４８．。Trioctyl trimellitate 48. .
この基本調合物を種々の安定剤組成物と混和することによって、種々の安定化さ れたＰＶＣ調合物の調合を行った。これらの安定化されたＰＶＣ調合物の組成を 以下の表１に示す。By blending this basic formulation with various stabilizer compositions, various stabilizing effects can be obtained. A PVC formulation was prepared. The composition of these stabilized PVC formulations is It is shown in Table 1 below.
表１ ’ Ｋｙｏｗａ Ｃｈｅｍｉｃａｌ Ｉｎｄｕｓｔｒｙ Ｃｏ、、Ｌｔｄが市販 している式 ％式％ で表される水滑石 ２ ＵＯＰが市販しているモレキュラーシーブゼオライト（平均孔サイズ−１３ オングストローム） ３ ＲＭｎｅ−Ｐｏｕ Ｉ ｅｎｃが市販しているジベンゾイルメタン’ ＩＣ Ｉ ５ｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓが市販している１、１． ３−ト リス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン抗酸化剤 ５７デカ・アーガス化学株式会社（Ａｄｅｋａ Ａｒｇｕｓ Ｃｈｅｍｉ−ｃａ ｌ Ｃｏ、、Ｌｔｄ）が市販しているバリウム／亜鉛安定剤’ Ｈａｌｓｔａ ｂが市販している三塩基性硫酸鉛’ Ａｎｚｏｎが市販している二塩基性フタル 酸鉛。Table 1 ’ Kyowa Chemical Industry Co, Ltd. formula %formula% hydrotalcite represented by 2 Molecular sieve zeolite commercially available from UOP (average pore size -13 angstrom) 3 Dibenzoylmethane' IC commercially available from RMne-Pou I enc 1, 1. commercially available from I5specialty Chemicals. 3-t Lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane antioxidant 57 Adeka Argus Chemi-ca Halsta is a barium/zinc stabilizer commercially available from Co., Ltd. Tribasic lead sulfate, commercially available from B; dibasic phthalate, commercially available from Anzon. Acid lead.
表１に示す安定化された組成物に、下記の条件下でグラベンダー安定性試験を受 けさせた。５００ヘツド、２００’ＣＣ１１Ｏ０ｒｐ、６８ｇ仕込み。その結果 を以下の表２に示す。The stabilized compositions shown in Table 1 were subjected to the Gravender stability test under the following conditions. I let it go. 500 head, 200'CC11O0rp, 68g preparation. the result are shown in Table 2 below.
゛ ２つの測定値の平均。゛゛ Average of two measurements.
表２のデータから分かるであろうように、本発明の水滑石／ゼオライト安定剤組 成物が入っているＰＶＣ調合物は、熱安定性の観点で好適に、鉛を基とする安定 剤のみが入っているＰＶＣ調合物に匹敵している。As can be seen from the data in Table 2, the hydrotalcite/zeolite stabilizer set of the present invention PVC formulations containing lead-based stabilizers are preferred from a thermal stability point of view. Comparable to PVC formulations containing only the agent.
実施例２ この実施例では、基本調合物と種々の安定剤組成物から１組の安定化されたＰＶ Ｃ調合物を製造し、そしてこれらの安定化されたＰＶＣ調合物にＭＥＴＳ−ＩＲ 試験を受けさせた。ＭＥＴＳ−Ｉ Ｒ試験は、平らな金属電極の回りにＰＶＣン ートを位置させて成形した後、この試験片を一定温度水浴の中に入れることを伴 っている。次に、この組成物が示す電気抵抗を測定するが、これは、ワイヤー上 （ｏｎ−ｗｉｒｅ）絶縁抵抗測定値に相関関係を示し得る。この試験は、部分的 には、絶縁抵抗特性に関するＵｎｄｅｒｗｒｉｔｅｒ’ ｓ Ｌａｂｏｒａｔｏ ｒｉｅｓＳｕｂｊｅｃｔ １５８１を基にしている。Example 2 In this example, a set of stabilized PVs was prepared from the base formulation and various stabilizer compositions. C formulations and METS-IR to these stabilized PVC formulations. made me take the test. The METS-IR test uses PVC wrap around a flat metal electrode. After positioning and shaping, the specimen is placed in a constant temperature water bath. ing. Next, the electrical resistance of this composition is measured, which is measured on the wire. (on-wire) Insulation resistance measurements can be correlated. This test is partially Underwriter's Laborato on insulation resistance characteristics It is based on riesSubject 1581.
この基本ＰＶＣ調合物は下記の組成を有していた。This basic PVC formulation had the following composition.
材料 ＰＨＲ ｐｖｃ樹脂 １００．０ トリメリツト酸トリオクチル ４６０ 粘土 ７．０ パラフインワツクス ０．３ 鉛安定剤を全く含有させないＰＶＣ調合物の場合の基本調合物には、下記も含有 させた・ 材料 Ｐ ＨＲ ＥＳＯ（エポキシ化大豆油）３．０ ステアリン酸Ｃａ １．５ ステアリン酸Ｚｎ ０．５ 以下の表３は、種々の安定剤を用いて製造した種々のＰＶＣ調合物に関するＭＥ ＴＳ−ＩＲ試験の結果を示している。Material PHR pvc resin 100.0 Trioctyl trimellitate 460 Clay 7.0 Parafine wax 0.3 For PVC formulations that do not contain any lead stabilizers, the basic formulation also contains: I let it happen. Material P HR ESO (epoxidized soybean oil) 3.0 Ca stearate 1.5 Zn stearate 0.5 Table 3 below shows the ME for various PVC formulations made with various stabilizers. The results of the TS-IR test are shown.
Ａ Ｄｙｔａｈｌ ＸＬ ７．０ ５４０２．７Ｂ Ｄ ＨＴ −４Ａ −２１ １，Ｑ ５４０９．３ＣＤＨＴ−４Ａ−２１，０３５４３，６Ｒｈｏｄｉａｓｔ ａｂ ８３ ０．２２Ｄ ＮａＸゼオライト２１．０ ３４６９．８Ｅ ＤＨＴ −４Ａ−２１，０６２６６，６ＮａＸゼオライト １．０ ’ Ｋｙｏｗａ Ｃｈｅｍｉｃａｌ Ｉｎｄｕｓｔｒｙ Ｃｏ、、Ｌｔｄが市販 している式 ％式％） て表される無水水滑石 ２ ＵＯＰが市販しているモレキュラーシーブゼオライト（平均孔サイズ−１３ オングストローム）。A Dytahl XL 7.0 5402.7B D HT -4A -21 1,Q 5409.3CDHT-4A-21,03543,6Rhodiast ab 83 0.22D NaX Zeolite 21.0 3469.8E DHT -4A-21,06266,6NaX zeolite 1.0 ’ Kyowa Chemical Industry Co, Ltd. formula %formula%) anhydrite expressed as 2 Molecular sieve zeolite commercially available from UOP (average pore size -13 Angstrom).
表３のデータから分かるであろうように、ゼオライトと水滑石との組み合わせは 、水滑石単独か、ゼオライト単独か、或は水滑石とベータージケトンに比較して 、優れたＭＥＴＳ−ＩＲ結果を与える。As can be seen from the data in Table 3, the combination of zeolite and hydrotalcite is , compared to hydrotalcite alone, zeolite alone, or hydrotalcite and beta-diketone. , giving excellent METS-IR results.
実施例３ 米国特許第４．４２７．８１６号に開示されている安定剤である鉛安定剤、およ び本発明の安定剤組成物を用いた、１組のＰＶＣ調合物に関して、体積抵抗測定 を実施した。安定化されたＰｖＣ調合物を製造する目的で、下記の基本調合物を 用いた： 材料 ｒ’ＨＲ ＰＶＣ崩脂 １０００ フタル酸シオタチル（ＤＯＰ） ５０．０ステアリン酸Ｚｎ ０．３ ステアリン酸Ｃａ Ｑ、７ この基本調合物を用いると共に種々の安定剤組成物を用いて、安定化されたＰｖ Ｃ調合物を調製した。この安定化されたＰＶＣ調合物の組成とＶＲ測定結果を以 下の表４に示す。Example 3 Lead stabilizers, which are stabilizers disclosed in U.S. Pat. No. 4,427,816; Volume resistivity measurements were performed on a set of PVC formulations using the stabilizer composition of the present invention. was carried out. For the purpose of producing a stabilized PvC formulation, the following basic formulation was Using: Material r’HR PVC fat loss 1000 Thiotatyl phthalate (DOP) 50.0 Zn stearate 0.3 Ca stearate Q, 7 Using this basic formulation and using various stabilizer compositions, stabilized Pv Formulation C was prepared. The composition and VR measurement results of this stabilized PVC formulation are as follows. It is shown in Table 4 below.
Ａ Ａｌｃａｍｉｚｅｒ １ １．０５ １．７Ｂ Ａｌｃａｍｉｚｅｒ １ １．０ １．８５Ｒｈｏｄｉａｓｔａｂ ８３ ０．０５ＣＮａＸゼオライト １．０５ １．２４Ｄ ＮａＸゼオライト １．０ Ｒｈｏｄｉａｓｔａｂ ８３ ０．０５ ０．９５Ｅ Ａｌｃａｍｉｚｅｒ １ ０．５２５ ３．１９ＮａＸゼオライｌ−０，，５２５ Ｆ Ａｌｃａｍｉｚｅｒ １ ０．５ ２．７４ＮａＸゼオライト ０．５ Ｒｈｏｄｉａｓｔａｂ ８３ ０．０５Ｇ Ｄｙｔａｈｌ ＸＬ ７．０ １． ５８実施例４ 種々の安定剤組成物を用いて１組の安定化されたＰＶＣ調合物を調製し、そして この安定化されち調合物の各々に関してＶＲデータを得た。A Alcamizer 1 1.05 1.7B Alcamizer 1 1.0 1.85Rhodiastab 83 0.05CNaX Zeolite 1.05 1.24D NaX zeolite 1.0 Rhodiastab 83 0.05 0.95E Alcamizer 1 0.525 3.19 NaX zeolite l-0,,525 F Alcamizer 1 0.5 2.74 NaX Zeolite 0.5 Rhodiastab 83 0.05G Dytahl XL 7.0 1. 58 Example 4 A set of stabilized PVC formulations was prepared using various stabilizer compositions, and VR data was obtained for each of the stabilized formulations.
この安定化された調合物の一造では、下記の基本調合物を用いた：材料 Ｐ Ｈ Ｒ ＰＶＣ…脂 １０００ ＤＯＰ ４５．０ ステアリン酸Ｚｎ Ｏ，２５ ステアリン酸Ｃａ ０．７５ 種々の安定化された調合物の組成およびＶＲ測定結果を以下の表５に示す。In making this stabilized formulation, the following basic formulation was used: Materials P H R PVC…fat 1000 DOP 45.0 Zn stearate O, 25 Ca stearate 0.75 The compositions and VR measurements of the various stabilized formulations are shown in Table 5 below.
＊ ４つのす／プルの平均。*Average of 4 su/pulls.
’ Ｚｅｏｃｈｅｍが市販しているモレキュラーシーブゼオライト（平均孔サイ ズ−４オングストローム） ” Ｚｅｏｃｈｅｍが市販しているモレキュラーシーブゼオライト（平均孔サイ ズ−５オングストローム） ３ ＵＯＰが市販しているモレキュラーシーブゼオライト（平均孔サイ表５のデ ータから分かるであろうように、水滑石とゼオライトとの組み合わせは＼ｒＲ測 定値に関して相乗性を示す。特に、このゼオライトの平均孔サイスが５オングス トロ一ム以上、好適には約１０オングストローム以上の時、例外的に高いＶＲ値 が得られる（調合物１４１Ｇおよび８４１−１と調合物８４Ｃとの比較）。これ に関して、ＮａＸゼオライトおよび１３Ｘゼオライトの孔サイズは両方とも約１ ３オングストロームであることに注目すべきである。表５のデータから分かるで あろうように、本発明の安定剤組成物’、１１、通常の鉛で安定化された調合物 （例えば調合物１０４Ｊを参照）を用いた時得られるよりもずっと良好なＶＲ測 定値を与える。本発明の安定剤組成物は、米国特許第４．４２７．８１６号の中 に開示されている安定剤組成物を用いた時得られるよりも良好なＶＲ値を与える ことも分かるであろう（例えば調合物１４７Ｃ１１４１Ｃおよび８４Ｅと調合物 １４１Ｇおよび８４Ｉ４との比較）。本発明の安定剤組成物の中にベータージケ トンを組み込むと増強されたＶＲ値を得ることができることも分かるであろう（ 例えば調合物１４７Ｇ、１４７Ｈおよび８４Ｇを参照）。’ Molecular sieve zeolite commercially available from Zeochem (average pore size 4 angstroms) ” Molecular sieve zeolite commercially available from Zeochem (average pore size 5 angstroms) 3 Molecular sieve zeolite commercially available from UOP (average pore size As can be seen from the data, the combination of hydrotalcite and zeolite is Shows synergy with respect to fixed values. In particular, the average pore size of this zeolite is 5 oz. Exceptionally high VR values when the trom is greater than 10 angstroms, preferably about 10 angstroms or greater is obtained (comparison of formulations 141G and 841-1 with formulation 84C). this Regarding, the pore size of NaX zeolite and 13X zeolite are both about 1 It should be noted that 3 angstroms. It can be seen from the data in Table 5 that As will be seen, the stabilizer composition of the present invention', 11, a conventional lead-stabilized formulation (see e.g. formulation 104J) Give a fixed value. The stabilizer compositions of the present invention are described in U.S. Pat. No. 4,427,816. give better VR values than obtained when using the stabilizer composition disclosed in It will also be seen that (e.g. formulations 147C1141C and 84E and formulations 141G and 84I4). In the stabilizer composition of the present invention, beta oxide is present. It will also be seen that enhanced VR values can be obtained by incorporating t ( See for example formulations 147G, 147H and 84G).
上のデータは明らかに、本発明の安定剤組成物を用いることによって、鉛安定剤 を用いなくても上記鉛含有調合物に相当する熱安定性を示すハロゲン含有ポリマ ー調合物を調合することができることを示している。The above data clearly shows that by using the stabilizer composition of the present invention, the lead stabilizer Halogen-containing polymers exhibiting thermal stability comparable to the lead-containing formulations described above, even without the use of – Indicates that the compound can be prepared.
更に、本発明の安定剤組成物を用いたポリマー調合物が示す電気特性は、鉛を基 とする安定剤を用いた時得られる電気特性と等しいか或はそれよりも優れている 。Additionally, the electrical properties of polymer formulations using the stabilizer compositions of the present invention are superior to those based on lead. The electrical properties are equal to or better than those obtained using stabilizers. .
上に示した本発明の開示および説明は、本発明を示しそして説明するものであり 、本発明の精神から逸脱しない限り添付請求の範囲内でこの組成に関して種々の 変更を行うことが可能である。The disclosure and description of the invention set forth above illustrates and describes the invention. , various modifications may be made to this composition within the scope of the appended claims without departing from the spirit of the invention. It is possible to make changes.
Claims (10)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US862,325 | 1992-04-02 | ||
| US07/862,325 US5216058A (en) | 1992-04-02 | 1992-04-02 | Stabilizer compositions for halogen-containing polymers and polymer compositions containing same |
| PCT/US1993/001686 WO1993020135A1 (en) | 1992-04-02 | 1993-02-25 | Stabilizer compositions for halogen-containing polymers and polymer compositions containing same |
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| JPH07505430A true JPH07505430A (en) | 1995-06-15 |
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| JP5517435A Pending JPH07505430A (en) | 1992-04-02 | 1993-02-25 | Stabilizer composition for halogen-containing polymers and the above-mentioned containing polymer composition |
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| Country | Link |
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| US (1) | US5216058A (en) |
| EP (1) | EP0633908A4 (en) |
| JP (1) | JPH07505430A (en) |
| MX (1) | MX9301897A (en) |
| WO (1) | WO1993020135A1 (en) |
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| DE59308266D1 (en) * | 1992-05-13 | 1998-04-23 | Ciba Geigy Ag | Stabilized chlorine-containing polymer compositions |
| US5582873A (en) * | 1994-08-04 | 1996-12-10 | Carol M. Botsolas | Acid scavenger stabilized halogen containing organic polymers and method for processing |
| US5739188A (en) * | 1994-10-14 | 1998-04-14 | Desai; Nirav | Thermoplastic polymer compositions with improved processability and method of processing |
| US5872166A (en) * | 1995-06-20 | 1999-02-16 | Witco Corporation | Overbased PVC stabilizer |
| TW411352B (en) * | 1995-06-30 | 2000-11-11 | Witco Vinyl Additives Gmbh | Composition of containing a stabilised halogen-containing polymer |
| EP0962491B1 (en) | 1998-06-02 | 2003-06-04 | Crompton Vinyl Additives GmbH | Cyanacetylurea to stabilize halogenated polymers |
| EP0967209B1 (en) | 1998-06-26 | 2003-01-08 | Crompton Vinyl Additives GmbH | NH2-modified 6-aminouracils as stabilisers for halogen-containing polymers |
| EP0967245A1 (en) | 1998-06-26 | 1999-12-29 | Witco Vinyl Additives GmbH | 1,3 substituted 6-aminouraciles to stabilize halogenated polymers |
| US6306945B1 (en) | 1998-09-10 | 2001-10-23 | Pmd Holdings Corporation | Halogen containing polymer compounds containing modified zeolite stabilizers |
| US6180549B1 (en) | 1998-09-10 | 2001-01-30 | The B. F. Goodrich Company | Modified zeolites and methods of making thereof |
| US6531526B1 (en) | 1998-09-10 | 2003-03-11 | Noveon Ip Holdings Corp. | Halogen containing polymer compounds containing modified zeolite stabilizers |
| DE19915388A1 (en) | 1999-04-06 | 2000-10-12 | Witco Vinyl Additives Gmbh | 4-aminopyrimidinones and oxazolidino-4-aminopyrimidinones, processes for their preparation and their use for stabilizing halogen-containing polymers |
| US6414071B1 (en) | 1999-07-29 | 2002-07-02 | Pq Corporation | Aluminosilicate stabilized halogenated polymers |
| US6096820A (en) * | 1999-07-29 | 2000-08-01 | Pq Corporation | Aluminosilicate stabilized halogenated polymers |
| US6225387B1 (en) | 2000-02-17 | 2001-05-01 | Great Lakes Chemical Corporation | Stabilizer blend for organic polymer compositions; stabilized polymer compositions and method of stabilizing polymers |
| US8257782B2 (en) * | 2000-08-02 | 2012-09-04 | Prysmian Cavi E Sistemi Energia S.R.L. | Electrical cable for high voltage direct current transmission, and insulating composition |
| US7312266B2 (en) * | 2000-12-15 | 2007-12-25 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
| US6667357B2 (en) | 2000-12-15 | 2003-12-23 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
| US6927247B2 (en) * | 2000-12-15 | 2005-08-09 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
| US6762231B2 (en) | 2000-12-15 | 2004-07-13 | The College Of William And Mary | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers |
| ES2233711T3 (en) | 2001-02-16 | 2005-06-16 | Crompton Vinyl Additives Gmbh | NEW STABILIZER SYSTEM FOR THE STABILIZATION OF POLYMERS CONTAINING HALOGENS. |
| US6979708B2 (en) * | 2001-08-23 | 2005-12-27 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
| US6846870B2 (en) * | 2001-08-23 | 2005-01-25 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
| US7282527B2 (en) | 2003-08-19 | 2007-10-16 | Crompton Corporation | Stabilization system for halogen-containing polymers |
| US20090022462A1 (en) * | 2007-07-20 | 2009-01-22 | Polymer Products Company, Inc. | Fire resistant jacket composition for electrical coaxial and fiber optic cable |
| DE102008018872A1 (en) | 2008-04-14 | 2009-10-15 | Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg | Stabilizer system for halogen-containing polymers |
| EP2123659A1 (en) | 2008-05-15 | 2009-11-25 | Arkema France | High purity monoalkyltin compounds and uses thereof |
| US8354462B2 (en) | 2009-11-30 | 2013-01-15 | Chemson Polymer Additives AG | Heat stabilizers containing hydrotalcite particles with specific zeta potentials that demonstrate improved processing and performance in molded vinyl compounds |
| DE102010008854A1 (en) | 2010-02-22 | 2011-08-25 | IKA Innovative Kunststoffaufbereitung GmbH & Co. KG, 06766 | Stabilizer system for foamable halogen-containing polymers |
| US8507596B2 (en) | 2011-02-18 | 2013-08-13 | Galata Chemicals Llc | Bio-based plasticizer |
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| FR2986003B1 (en) | 2012-01-24 | 2015-01-16 | Arkema France | PROCESS FOR THE PREPARATION OF HALOGEN POLYMERS |
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| WO2014122075A1 (en) | 2013-02-05 | 2014-08-14 | Basf Se | Lubricant compositions for thermoplastic polymers |
| MY192621A (en) | 2015-10-23 | 2022-08-29 | Akdeniz Chemson Additive Ag | Vinyl chloride polymers and compositions for additive manufacturing |
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| DE112023000623T5 (en) | 2022-01-19 | 2024-11-14 | Galata Chemicals Gmbh | HEAT STABILIZER FOR CHLORINE-CONTAINING POLYMERS |
| WO2024039661A1 (en) | 2022-08-15 | 2024-02-22 | Galata Chemicals Llc | Processable polyvinyl chloride compounds |
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| US4000100A (en) * | 1971-06-04 | 1976-12-28 | W. R. Grace & Co. | Thermal and light stabilized polyvinyl chloride resins |
| JPS5818939B2 (en) * | 1977-08-24 | 1983-04-15 | 水「沢」化学工業株式会社 | Method for thermal stabilization of chlorine-containing polymers |
| JPS6045657B2 (en) * | 1980-07-23 | 1985-10-11 | 日本化学工業株式会社 | Stabilizer for chlorine-containing resins |
| JPS5836012B2 (en) * | 1980-11-07 | 1983-08-06 | アデカ・ア−ガス化学株式会社 | Halogen-containing resin composition |
| JPS57177033A (en) * | 1981-04-23 | 1982-10-30 | Kosei:Kk | Resin additive composition |
| FR2628114B1 (en) * | 1988-03-07 | 1990-07-13 | M & T Chemicals Inc | COMPOSITION FOR USE IN THE THERMAL AND ULTRAVIOLET STABILIZATION OF THERMOPLASTIC RESINS AND THERMOPLASTIC RESINS CONTAINING SUCH A STABILIZING COMPOSITION |
| JPH01247427A (en) * | 1988-03-29 | 1989-10-03 | Idemitsu Petrochem Co Ltd | Polypropylene film |
| JPH07709B2 (en) * | 1989-04-27 | 1995-01-11 | 昭島化学工業株式会社 | Thermally stabilized chlorine-containing resin composition |
| US5141980A (en) * | 1989-06-23 | 1992-08-25 | Elf Atochem North America, Inc. | Composition usable for the thermal and ultaviolet stabilization of thermoplastic resins and thermoplastic resins containing such a stabilizing composition |
| JP2758031B2 (en) * | 1989-07-04 | 1998-05-25 | 協和化学工業株式会社 | Stabilizer composition for halogen-containing resin |
-
1992
- 1992-04-02 US US07/862,325 patent/US5216058A/en not_active Expired - Fee Related
-
1993
- 1993-02-25 WO PCT/US1993/001686 patent/WO1993020135A1/en not_active Application Discontinuation
- 1993-02-25 JP JP5517435A patent/JPH07505430A/en active Pending
- 1993-02-25 EP EP93907035A patent/EP0633908A4/en not_active Withdrawn
- 1993-04-01 MX MX9301897A patent/MX9301897A/en unknown
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| Publication number | Publication date |
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| EP0633908A1 (en) | 1995-01-18 |
| EP0633908A4 (en) | 1996-06-05 |
| US5216058A (en) | 1993-06-01 |
| MX9301897A (en) | 1994-02-28 |
| WO1993020135A1 (en) | 1993-10-14 |
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